JP4578714B2 - N-vinyl-2-pyrrolidone-containing resin composition, process for producing the same, and cosmetic comprising the same - Google Patents

Description

【００１１】
で表わされるＮ−ビニル−２−ピロリドン（Ａ）０．１〜１００重量％および該Ｎ−ビニル−２−ピロリドン（Ａ）と共重合可能なエチレン性不飽和二重結合含有モノマー（Ｂ）９９．９〜０重量％を含有したモノマー成分を共重合させて得られる共重合体からなる樹脂組成物の製法において、
前記モノマー成分を共重合させるあいだ、または共重合させたのちに、該モノマー成分１００重量部に対して０．０００１〜２０重量部の還元性化合物（Ｃ）を添加することを特徴とするＮ−ビニル−２−ピロリドン含有樹脂組成物の製法、
▲２▼前記製法にて製造されたＮ−ビニル−２−ピロリドン含有樹脂組成物、および
▲３▼前記Ｎ−ビニル−２−ピロリドン含有樹脂組成物が配合されてなる化粧料
に関する。
【００１２】
【発明の実施の形態】
本発明のＮ−ビニル−２−ピロリドン含有樹脂組成物（以下、単に樹脂組成物ともいう）の製法は、前記したように、式（Ｉ）：
【００１３】
【化３】

【００１４】
で表わされるＮ−ビニル−２−ピロリドン（Ａ）０．１〜１００重量％および該Ｎ−ビニル−２−ピロリドン（Ａ）と共重合可能なエチレン性不飽和二重結合含有モノマー（Ｂ）（以下、モノマー（Ｂ）という）９９．９〜０重量％を含有したモノマー成分を共重合させるあいだ、または共重合させたのちに、該モノマー成分１００重量部に対して０．０００１〜２０重量部の還元性化合物（Ｃ）を添加することを特徴とするものである。
【００１５】
前記Ｎ−ビニル−２−ピロリドン（Ａ）は、得られる樹脂組成物から形成される皮膜に適度な硬度および光沢を付与し得る成分である。
【００１６】
前記Ｎ−ビニル−２−ピロリドン（Ａ）と共重合されるモノマー（Ｂ）は、たとえば化粧料の基材としての水溶性、油溶性、べたつき感抑制、すべり感、乾き感、自然感、造膜性、粘性、透明感、ガス相溶性、ガス透過性、他の添加剤との相溶性といった効果を、樹脂組成物に付与し得るモノマーであり、目的とする樹脂組成物の用途などに応じて適宜その種類を選択して用いることができる。
【００１７】
前記モノマー（Ｂ）の代表例としては、たとえば（メタ）アクリル酸；（メタ）アクリル酸のアルカリ金属塩、（メタ）アクリル酸のアンモニウム塩などの（メタ）アクリル酸塩；（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸ネオペンチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸オクチル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸セチル、（メタ）アクリル酸テトラヒドロフルフリル、（メタ）アクリル酸エチルカルビトール、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチル、（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸メトキシブチルなどの（メタ）アクリル酸エステル；（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ−エチル（メタ）アクリルアミド、Ｎ−ｎ−プロピル（メタ）アクリルアミド、Ｎ−イソプロピル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、Ｎ−ｔ−ブチル（メタ）アクリルアミド、Ｎ−オクチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチル（メタ）アクリルアミドなどのアルキル（メタ）アクリルアミド；（メタ）アクリロイルモルホリン；Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレートおよびその３級塩およびその４級塩、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレートおよびその３級塩およびその４級塩、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレートおよびその３級塩およびその４級塩、Ｎ，Ｎ−ジエチルアミノプロピル（メタ）アクリレートおよびその３級塩およびその４級塩、Ｎ−ｔ−ブチルアミノエチル（メタ）アクリレートおよびその３級塩およびその４級塩、Ｎ−ｔ−ブチルアミノプロピル（メタ）アクリレートおよびその３級塩およびその４級塩などのアミノアルキル（メタ）アクリレートおよびその塩；Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリルアミドおよびその３級塩およびその４級塩、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミドおよびその３級塩およびその４級塩、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリルアミドおよびその３級塩およびその４級塩、Ｎ，Ｎ−ジエチルアミノプロピル（メタ）アクリルアミドおよびその３級塩およびその４級塩などのアミノアルキル（メタ）アクリルアミドおよびその塩；Ｎ−（メタ）アクリロイルオキシメチル−Ｎ，Ｎ−ジメチルアンモニウム−α−Ｎ−カルボキシベタイン、Ｎ−（メタ）アクリロイルオキシエチル−Ｎ，Ｎ−ジメチルアンモニウム−α−Ｎ−カルボキシベタイン、Ｎ−（メタ）アクリロイルオキシプロピル−Ｎ，Ｎ−ジメチルアンモニウム−α−Ｎ−カルボキシベタイン、Ｎ−（メタ）アクリロイルオキシメチル−Ｎ，Ｎ−ジエチルアンモニウム−α−Ｎ−カルボキシベタイン、Ｎ−（メタ）アクリロイルオキシエチル−Ｎ，Ｎ−ジエチルアンモニウム−α−Ｎ−カルボキシベタイン、Ｎ−（メタ）アクリロイルオキシプロピル−Ｎ，Ｎ−ジエチルアンモニウム−α−Ｎ−カルボキシベタインなどのベタイン類；ジアセトン（メタ）アクリルアミド、スチレン、イタコン酸、イタコン酸メチル、イタコン酸エチル、酢酸ビニル、プロピオン酸ビニルなどの単官能モノマーがあげられるほか、たとえば１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、２−ｎ−ブチル−２−エチル−１，３−プロパンジオールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレートなどのジ（メタ）アクリレート；トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレートなどのトリ（メタ）アクリレート；メチレンビスアクリルアミドなどの多官能モノマーなどがあげられ、これらは単独でまたは２種以上を混合して用いることができる。
【００１８】
なお本明細書において「…（メタ）アクリ〜」は「…アクリ〜」および「…メタクリ〜」を意味する。
【００１９】
Ｎ−ビニル−２−ピロリドン（Ａ）とモノマー（Ｂ）との割合は、該Ｎ−ビニル−２−ピロリドン（Ａ）による効果を考慮して決定され、樹脂組成物から形成される皮膜に適度な硬度および光沢が付与されるように、Ｎ−ビニル−２−ピロリドン（Ａ）がモノマー成分の０．１重量％以上、好ましくは１０重量％以上、すなわちモノマー（Ｂ）がモノマー成分の９９．９重量％以下、好ましくは９０重量％以下となるように調整される。また水溶性、油溶性、べたつき感抑制、すべり感、乾き感、自然感、造膜性、粘性、透明感、ガス相溶性、ガス透過性、他の添加剤との相溶性といったモノマー（Ｂ）による効果が充分に発現されるようにするには、モノマー（Ｂ）がモノマー成分の好ましくは５重量％以上、さらに好ましくは１０重量％以上、すなわちＮ−ビニル−２−ピロリドン（Ａ）がモノマー成分の好ましくは９５重量％以下、さらに好ましくは９０重量％以下となるように調整される。
【００２０】
前記共重合体を製造するには、Ｎ−ビニル−２−ピロリドン（Ａ）およびモノマー（Ｂ）の量をそれぞれ調整したモノマー成分を共重合させるが、このモノマー成分を共重合させるあいだ、または共重合させたのちに、還元性化合物（Ｃ）を添加する。
【００２１】
前記還元性化合物（Ｃ）を添加することにより、Ｎ−ビニル−２−ピロリドン（Ａ）の分解物の誘導体に起因すると推定される臭気が充分に低減された樹脂組成物を、ポリマー溶液の状態で容易に得ることができる。
【００２２】
還元性化合物（Ｃ）の代表例としては、たとえば水素；一酸化炭素；二酸化硫黄；亜硫酸ナトリウム、亜硫酸水素ナトリウムなどの亜硫酸塩；硫化ナトリウム；ヒドロキシアミン類；アルカリ金属、マグネシウム、カルシウム、アルミニウム、亜鉛などの金属や該金属のアマルガム；鉄（II）、スズ（II）チタン（III）、クロム（II）などの金属の塩類；アルデヒド類；マルトースなどの還元糖；ギ酸；シュウ酸；アスコルビン酸などがあげられ、これらは単独でまたは２種以上を混合して用いることができる。これらのなかでは、得られる樹脂組成物をたとえば化粧料などの人体に付着させる用途のものに配合することを考慮すると、安全性が高いことが好ましいという点から水素、亜硫酸塩および還元糖がとくに好ましい。
【００２３】
添加される還元性化合物（Ｃ）の量は、還元効果を充分に発現させるには、モノマー成分１００重量部に対して０．０００１重量部以上、好ましくは０．０１重量部以上となるように調整し、また得られるポリマー溶液中に還元性化合物（Ｃ）が多量に残存し、ポリマー溶液の毒性が上昇しないようにするには、モノマー成分１００重量部に対して２０重量部以下、好ましくは１０重量部以下となるように調整する。
【００２４】
還元性化合物（Ｃ）を添加する時期は、モノマー成分を共重合させているあいだであってもよく、モノマー成分を共重合させたのちであってもよいが、共重合初期には還元性化合物（Ｃ）が成長ラジカルの寿命を短縮するおそれがあることから、共重合開始から１時間以降、好ましくは３時間以降に還元性化合物（Ｃ）を添加することが望ましい。またモノマー成分を共重合させたのちに還元性化合物（Ｃ）を添加する際、共重合系の重合温度を上昇させていた場合には、該共重合系を適宜冷却させてもよい。
【００２５】
なお前記モノマー成分の共重合は、該モノマー成分を水溶液としたり、有機溶剤中にて行なうことができる。すなわち、所望組成のモノマー成分を精製水や有機溶剤に充分に溶解させ、これを必要に応じて加熱撹拌しながら重合開始剤を添加し、不活性ガス雰囲気下で共重合を行なうなどすればよい。
【００２６】
前記有機溶剤にはとくに限定がなく、たとえばメチルアルコール、エチルアルコール、イソプロピルアルコール、エチレングリコール、プロピレングリコールなどのアルコール類；アセトン、メチルエチルケトンなどのケトン類；ジエチルエーテル、テトラヒドロフランなどのエーテル類；ベンゼン、トルエン、キシレンなどの芳香族類；ｎ−ヘキサン、シクロヘキサンなどの炭化水素類；酢酸メチル、酢酸エチルなどの酢酸エステル類などの通常溶液重合に用いられる有機溶剤を使用することができる。これらのなかでは、得られる樹脂組成物を化粧料に配合することを考慮すると、エチルアルコール、イソプロピルアルコールなどのアルコール類がとくに好ましい。
【００２７】
なお前記水溶液や有機溶剤中で共重合を行なう場合、モノマー成分の濃度が１０〜８０重量％程度となるように調整することが好ましい。
【００２８】
前記重合開始剤にもとくに限定がなく、たとえばアゾイソブチロニトリル、アゾイソ酪酸メチル、アゾビスジメチルバレロニトリル、ジメチルアゾビスメチルプロピオネートなどのアゾ系重合開始剤；過酸化ベンゾイルなどの過酸化物系重合開始剤；過硫酸カリウム、過硫酸アンモニウムなどの過硫酸塩系重合開始剤などを用いることができる。該重合開始剤の量は、通常モノマー成分全量１００重量部に対して０．０１〜５重量部程度であればよい。
【００２９】
共重合を行なう際の重合温度は、用いる重合開始剤の種類によっても異なるので一概には決定することができないが、通常重合開始剤の１０時間半減期温度付近とすることが好ましい。また共重合を行なう際の重合時間は、共重合が不完全となって未反応のＮ−ビニル−２−ピロリドン（Ａ）および／またはモノマー（Ｂ）が残存するおそれをなくすには、通常５〜２０時間程度とすることが好ましい。
【００３０】
なお未反応モノマーの有無は、たとえばＰＳＤＢ法（二臭化硫酸ピリジン法）などの一般的な分析方法により、二重結合が存在するか否かを測定して確認することができる。
【００３１】
かくして得られる共重合体の粘度平均分子量にはとくに限定がないが、樹脂組成物が経皮吸収を起こすおそれがないように、１０００程度以上、好ましくは５０００程度以上であることが望ましく、使用性がわるくならないように、３００００００程度以下、好ましくは１５０００００程度以下であることが望ましい。
【００３２】
本発明の製法により製造される樹脂組成物は、従来のＮ−ビニルピロリドン系樹脂のような特有の臭気がいちじるしく低減されたものであり、しかも適度の硬度および光沢を有する皮膜を形成させることができるので、たとえば人体用の化粧料に好適に使用することができる。
【００３３】
本発明の化粧料は前記樹脂組成物が配合されてなるものである。かかる化粧料の種類にはとくに限定がないが、該樹脂組成物による効果を考慮すると、たとえば頭皮・頭髪用化粧料などがあげられる。
【００３４】
前記頭皮・頭髪用化粧料としては、たとえばヘアトニック、ポマード、ヘアスプレー、ヘアミスト、ムース、ジェル、ヘアワックス、シャンプー、リンス、トリートメント、ヘアクリームなどがあげられる。
【００３５】
本発明の化粧料における前記樹脂組成物の量にはとくに限定がなく、樹脂組成物による効果が充分に発現される量であればよいが、通常の化粧料における有効成分の含有量程度、たとえば１〜５０重量％程度、好ましくは３〜３０重量％程度であることが望ましい。
【００３６】
本発明の化粧料には樹脂組成物のほかに、化粧料の種類や目的に応じ、通常化粧料に配合される任意の成分、たとえば乳化剤、香料、防腐剤、顔料、栄養剤、保湿剤、紫外線防止剤、育毛剤などや、精製水などを常法にしたがって適宜配合することができる。
【００３７】
かくして得られる本発明の化粧料は、前記樹脂組成物を含有したものであるので、従来のＮ−ビニルピロリドン系樹脂のような特有の臭気がいちじるしく低減され、しかも適度の硬度および光沢を有する皮膜を形成させることができる。
【００３８】
【実施例】
つぎに、本発明のＮ−ビニル−２−ピロリドン含有樹脂組成物、その製法およびそれからなる化粧料を実施例に基づいてさらに詳細に説明するが、本発明はかかる実施例のみに限定されるものではない。
【００３９】
実施例１
還流冷却器、温度計、チッ素ガス導入管および撹拌装置を取り付けた１Ｌ容の反応容器に、Ｎ−ビニル−２−ピロリドン１００ｇおよび無水エタノール１５０ｇを添加し、さらに２，２´−アゾビスイソブチロニトリル０．１ｇおよび過硫酸アンモニウム０．０５ｇを添加し、撹拌しながらチッ素ガス気流下にて７８〜８０℃で６時間加熱し、重合反応を行なった。
【００４０】
ついで、この重合反応系に精製水２５０ｇを添加して加熱し、２５０ｇの溶媒を濃縮したのち、新たに精製水２５０ｇを添加してポリマー溶液を得た。このポリマー溶液を５０℃まで冷却し、亜硫酸水素ナトリウム０．５ｇを添加して撹拌し、２０重量％濃度のポリマー溶液（樹脂組成物）を得た。
【００４１】
得られたポリマー溶液中の共重合体の粘度平均分子量は１８１０００であった。
【００４２】
実施例２
還流冷却器、温度計、チッ素ガス導入管および撹拌装置を取り付けた１Ｌ容の反応容器に、Ｎ−ビニル−２−ピロリドン８０ｇ、メタクリル酸ヒドロキシプロピル２０ｇおよび精製水３００ｇを添加して均一な溶液としたのち、さらにアゾビスジメチルバレロニトリル０．３ｇを添加し、撹拌しながらチッ素ガス気流下にて６５〜７０℃で５時間加熱し、重合反応を行なった。
【００４３】
ついで、この重合反応系にヒドロキシアミン０．５ｇおよび精製水２００ｇを添加し、均一になるまで撹拌したのち、減圧にして１００ｇの水を濃縮し、２０重量％濃度のポリマー溶液（樹脂組成物）を得た。
【００４４】
得られたポリマー溶液中の共重合体の粘度平均分子量は５９００００であった。
【００４５】
実施例３
実施例２と同様にして重合反応を行なった。
【００４６】
ついで、この重合反応系に５％パラジウム炭素（５０％湿結）０．１ｇを添加し、水素により０．００５ＭＰａまで反応容器を加圧し、２５℃にて５時間撹拌した。こののち、この重合反応系を濾過し、２０重量％濃度のポリマー溶液（樹脂組成物）を得た。
【００４７】
得られたポリマー溶液中の共重合体の粘度平均分子量は５９００００であった。
【００４８】
実施例４
還流冷却器、温度計、チッ素ガス導入管および撹拌装置を取り付けた１Ｌ容の反応容器に、Ｎ−ビニル−２−ピロリドン５０ｇ、Ｎ，Ｎ−ジメチルアミノエチルメタクリレート２０ｇ、Ｎ−メタクリロイルオキシエチル−Ｎ，Ｎ−ジメチルアンモニウム−α−Ｎ−メチルカルボキシベタイン３０ｇおよび精製水２５０ｇを添加して均一な溶液としたのち、さらにジメチル−２，２−アゾビス（２−メチルプロピオネート）０．５ｇを添加し、撹拌しながらチッ素ガス気流下にて７０℃で重合反応を行ない、重合１０時間後に精製水３００ｇを添加した。
【００４９】
ついで、この重合反応系を減圧にして１５０ｇの水を濃縮し、アスコルビン酸１ｇを添加して均一に撹拌し、２０重量％濃度のポリマー溶液（樹脂組成物）を得た。
【００５０】
得られたポリマー溶液中の共重合体の粘度平均分子量は４７７０００であった。
【００５１】
実施例５
還流冷却器、温度計、チッ素ガス導入管および撹拌装置を取り付けた１Ｌ容の反応容器に、Ｎ−ビニル−２−ピロリドン７０ｇ、アクリル酸ｎ−ブチル１５ｇ、メタクリル酸ステアリル１５ｇおよび無水エタノール１５０ｇを添加して均一な溶液としたのち、さらに２，２´−アゾビスイソブチロニトリル０．５ｇを添加し、撹拌しながらチッ素ガス気流下にて７０℃で重合反応を行ない、重合３時間後にベンゾイルパーオキサイド０．３ｇを添加してさらに５時間重合反応を行なった。
【００５２】
ついで、この重合反応系に精製水２００ｇを添加し、均一になるまで撹拌したのち、減圧にして２００ｇの水を濃縮した。こののち、マルトース５ｇを添加して均一に撹拌し、２０重量％濃度のポリマー溶液（樹脂組成物）を得た。
【００５３】
得られたポリマー溶液中の共重合体の粘度平均分子量は１３４０００であった。
【００５４】
比較例１
還流冷却器、温度計、チッ素ガス導入管および撹拌装置を取り付けた１Ｌ容の反応容器に、Ｎ−ビニル−２−ピロリドン１００ｇおよび無水エタノール１００ｇを添加して均一な溶液としたのち、さらに２，２´−アゾビスイソブチロニトリル０．２ｇを添加し、撹拌しながらチッ素ガス気流下にて７０℃で１０時間加熱し、重合反応を行なった。
【００５５】
ついで、この重合反応系に精製水２００ｇを添加して均一な溶液としたのち、減圧にて２００ｇの溶媒を濃縮した。こののち精製水３００ｇを添加して均一に撹拌し、２０重量％濃度のポリマー溶液（樹脂組成物）を得た。
【００５６】
得られたポリマー溶液中の共重合体の粘度平均分子量は１５３０００であった。
【００５７】
比較例２
還流冷却器、温度計、チッ素ガス導入管および撹拌装置を取り付けた１Ｌ容の反応容器に、Ｎ−ビニル−２−ピロリドン９０ｇ、ダイアセトンアクリルアミド１０ｇおよび精製水４００ｇを添加して均一な溶液としたのち、さらにアゾビスジメチルバレロニトリル０．１ｇおよび過硫酸カリウム０．１ｇを添加し、撹拌しながらチッ素ガス気流下にて７０℃で１０時間加熱し、重合反応を行なった。
【００５８】
ついで、この重合反応系から減圧にて２００ｇの溶媒を濃縮したのち、新たに精製水２００ｇを添加し、２０重量％濃度のポリマー溶液（樹脂組成物）を得た。
【００５９】
得られたポリマー溶液中の共重合体の粘度平均分子量は６９９０００であった。
【００６０】
試験例１
実施例１〜５および比較例１〜２にて得られた２０重量％濃度のポリマー溶液と、これら２０重量％濃度のポリマー溶液を精製水で１０倍に希釈した２重量％濃度のポリマー溶液を用い、臭気について官能試験を行なった。
【００６１】
１００ｍＬ容のガラス製広口サンプル瓶に前記各ポリマー溶液５０ｍＬを入れ、無作為に抽出した男女計２０名の各パネラーに、瓶口での臭気を確認して以下の評価基準に基づいて評価してもらった。その評価人数に応じて以下に示すＡ、Ｂ、Ｃ、Ｄ、Ｅのランク付けを行なった。その結果を表１に示す。
［評価基準］
○：ほぼ無臭である。
△：やや焦げくさい。
×：焦げくさい臭いが強い。
［ランク］
Ａ：評価○が１５名以上であり、評価×がいない。
Ｂ：評価○が１５〜１９名であり、評価×が１〜５名である。
Ｃ：評価○が１０〜１４名であり、評価×が１〜１０名である。
Ｄ：評価○が５〜９名であり、評価×が１〜１５名である。
Ｅ：評価○が４名以下であり、評価×が１〜１６名である。
【００６２】
【表１】

【００６３】
表１に示された結果から、実施例１〜５で得られたポリマー溶液は、２０重量％濃度のものおよび２重量％濃度のものいずれも、ほぼ無臭であり、還元性化合物（Ｃ）が添加されているので、Ｎ−ビニル−２−ピロリドン（Ａ）の分解物の誘導体に起因すると推定される臭気が充分に低減されていることがわかる。
【００６４】
これに対し、還元性化合物（Ｃ）が用いられていない比較例１〜２のポリマー溶液は、濃度が２重量％のものであっても、Ｎ−ビニル−２−ピロリドン（Ａ）の分解物の誘導体特有の焦げくさい臭いがかなり認められ、還元性化合物（Ｃ）を添加しなければ低臭気の樹脂組成物を得ることができないことが明らかである。
【００６５】
処方例１［頭皮・頭髪用化粧料（ムース）］
以下に示す各成分を室温（約２４℃）にて撹拌混合し、原液を調製した。
【００６６】

【００６７】
つぎに、前記原液をエアゾール用耐圧容器（満注量：１００ｍＬ）内に充填し、さらに噴射剤として液化石油ガスを充填した［原液と噴射剤との割合（原液／噴射剤（重量比））＝９０／１０］。これにエアゾールバルブおよびボタンを取り付けてエアゾール型頭皮・頭髪用化粧料の製品を製造した。
【００６８】
得られたエアゾール型頭皮・頭髪用化粧料を通常の使用方法にて適量噴射させて手のひらに泡を取り、頭髪に塗布した。その結果、手のひらおよび頭髪に焦げくさい臭いは認められなかった。
【００６９】
処方例２［頭皮・頭髪用化粧料（ローション）］
以下に示す各成分を室温（約２４℃）にて撹拌混合し、ローション型頭皮・頭髪用化粧料を調製した。
【００７０】

【００７１】
つぎに、前記ローション型頭皮・頭髪用化粧料をボトルタイプのヘアーローション容器（内容量：１００ｍＬ）内に充填し、ローション型頭皮・頭髪用化粧料の製品を作製した。
【００７２】
得られたローション型頭皮・頭髪用化粧料を通常の使用方法にて頭髪に適量塗布させたが、焦げくさい臭いは認められなかった。
【００７３】
【発明の効果】
本発明の製法によれば、Ｎ−ビニル−２−ピロリドンに起因する特有の臭気を充分に低減させることができるので、該製法にて製造されたＮ−ビニル−２−ピロリドン含有樹脂組成物は低臭気であり、また該Ｎ−ビニル−２−ピロリドン含有樹脂組成物が配合された化粧料もやはり低臭気であり、たとえば頭髪・頭皮用化粧料として好適である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an N-vinyl-2-pyrrolidone-containing resin composition, a production method thereof, and a cosmetic comprising the same. More specifically, a method for producing an N-vinyl-2-pyrrolidone-containing resin composition capable of reducing a specific odor caused by N-vinyl-2-pyrrolidone, and a low-odor resin composition produced by the production method And a cosmetic that can be suitably used for hair and scalp, for example.
[0002]
[Prior art]
Conventionally, a resin containing N-vinylpyrrolidone has been widely used in cosmetics, particularly hair cosmetics. Such a resin containing N-vinylpyrrolidone can form a film having moderate hardness and gloss, and these moderate hardness and gloss are suitable physical properties for cosmetics for hair.
[0003]
However, a resin containing N-vinylpyrrolidone may emit a specific odor depending on the purity of the raw material N-vinylpyrrolidone and the production conditions of the resin. This unique odor is presumed to be caused by a derivative of N-vinylpyrrolidone degradation product, but the causative substance and its generation route are not clear.
[0004]
In order to deodorize such a specific odor, when the resin having the above-mentioned specific odor is blended in cosmetics, there is a possibility of harming the user's mood, and the product value as a cosmetic may be lowered. Although an azeotropic treatment with a solvent and an adsorption treatment with activated carbon have been attempted, a sufficient deodorizing effect has not been obtained.
[0005]
Thus, as an effective method for solving the above problem, there is a conventional method of obtaining a resin by spray drying. The resin containing N-vinylpyrrolidone obtained by spray drying is in the form of a powder, and has an advantage that the odor is relatively small when the powder is dissolved again in the solution.
[0006]
However, in order to perform the spray drying, it is necessary that the resin has a low molecular weight as much as possible, which limits a polymer that can be produced. Moreover, in order to mix | blend the said powder with cosmetics, it must be dissolved again in a solution, and an operation | work is complicated. In addition, dust explosion may occur during the charging operation, and the spray drying is not a suitable method for obtaining a resin containing N-vinylpyrrolidone.
[0007]
Therefore, development of a method capable of obtaining the resin containing N-vinylpyrrolidone in a solution state while suppressing a specific odor has been awaited.
[0008]
[Problems to be solved by the invention]
The present invention has been made in view of the above prior art, and has been produced by a method for producing an N-vinylpyrrolidone-containing resin composition capable of reducing a peculiar odor caused by N-vinylpyrrolidone. It is an object of the present invention to provide a low odor resin composition and a cosmetic containing the resin composition.
[0009]
[Means for Solving the Problems]
The present invention
(1) Formula (I):
[0010]
[Chemical formula 2]

[0011]
N-vinyl-2-pyrrolidone (A) represented by the formula: 0.1 to 100% by weight and an ethylenically unsaturated double bond-containing monomer (B) 99 copolymerizable with the N-vinyl-2-pyrrolidone (A) In the process for producing a resin composition comprising a copolymer obtained by copolymerizing a monomer component containing 9 to 0% by weight,
During the copolymerization of the monomer component or after the copolymerization, 0.0001 to 20 parts by weight of the reducing compound (C) is added to 100 parts by weight of the monomer component. Method for producing vinyl-2-pyrrolidone-containing resin composition,
(2) N-vinyl-2-pyrrolidone-containing resin composition produced by the above production method, and
(3) Cosmetics comprising the N-vinyl-2-pyrrolidone-containing resin composition
About.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
As described above, the method for producing the N-vinyl-2-pyrrolidone-containing resin composition of the present invention (hereinafter also simply referred to as a resin composition) is represented by the formula (I):
[0013]
[Chemical 3]

[0014]
N-vinyl-2-pyrrolidone (A) represented by the formula: 0.1 to 100% by weight and an ethylenically unsaturated double bond-containing monomer (B) copolymerizable with the N-vinyl-2-pyrrolidone (A) ( Hereinafter, the monomer component containing 99.9 to 0% by weight of monomer (B) is copolymerized during or after the copolymerization, and 0.0001 to 20 parts by weight relative to 100 parts by weight of the monomer component The reducing compound (C) is added.
[0015]
The N-vinyl-2-pyrrolidone (A) is a component capable of imparting appropriate hardness and gloss to a film formed from the resulting resin composition.
[0016]
The monomer (B) copolymerized with the N-vinyl-2-pyrrolidone (A) is, for example, a water-soluble, oil-soluble, sticky feeling, slippery, dry, natural, It is a monomer that can impart effects such as film properties, viscosity, transparency, gas compatibility, gas permeability, and compatibility with other additives to the resin composition, depending on the intended use of the resin composition, etc. The type can be appropriately selected and used.
[0017]
Representative examples of the monomer (B) include, for example, (meth) acrylic acid; (meth) acrylic acid salts such as (meth) acrylic acid alkali metal salts and ammonium salts of (meth) acrylic acid; (meth) acrylic acid Methyl, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, neopentyl (meth) acrylate, cyclohexyl (meth) acrylate, (meta ) Benzyl acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cetyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethyl carbitol (meth) acrylate , Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ( T) (Meth) acrylic acid esters such as hydroxybutyl acrylate, methoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate; (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) Acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-octyl (meth) acrylamide, N, N Alkyl (meth) acrylamides such as dimethyl (meth) acrylamide and N, N-diethyl (meth) acrylamide; (meth) acryloylmorpholine; N, N-dimethylaminoethyl (meth) acrylate and its tertiary salt and its quaternary Salt, N, N-dimethyl Aminopropyl (meth) acrylate and its tertiary salt and its quaternary salt, N, N-diethylaminoethyl (meth) acrylate and its tertiary salt and its quaternary salt, N, N-diethylaminopropyl (meth) acrylate and its Tertiary salt and its quaternary salt, Nt-butylaminoethyl (meth) acrylate and its tertiary salt and its quaternary salt, Nt-butylaminopropyl (meth) acrylate and its tertiary salt and its 4 Aminoalkyl (meth) acrylates such as quaternary salts and salts thereof; N, N-dimethylaminoethyl (meth) acrylamide and quaternary salts thereof and quaternary salts thereof, N, N-dimethylaminopropyl (meth) acrylamide and thereof 3 And its quaternary salt, N, N-diethylaminoethyl (meth) acrylami And its tertiary salts and its quaternary salts, aminoalkyl (meth) acrylamides and their salts such as N, N-diethylaminopropyl (meth) acrylamide and its tertiary and quaternary salts; N- (meth) acryloyl Oxymethyl-N, N-dimethylammonium-α-N-carboxybetaine, N- (meth) acryloyloxyethyl-N, N-dimethylammonium-α-N-carboxybetaine, N- (meth) acryloyloxypropyl-N , N-dimethylammonium-α-N-carboxybetaine, N- (meth) acryloyloxymethyl-N, N-diethylammonium-α-N-carboxybetaine, N- (meth) acryloyloxyethyl-N, N-diethyl Ammonium-α-N-carboxybetaine, N- (meth) Betaines such as acryloyloxypropyl-N, N-diethylammonium-α-N-carboxybetaine; simple substances such as diacetone (meth) acrylamide, styrene, itaconic acid, methyl itaconate, ethyl itaconate, vinyl acetate, and vinyl propionate In addition to functional monomers, for example, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 2-n-butyl- Di (meth) acrylates such as 2-ethyl-1,3-propanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, Pentae Suritorutori (meth) tri (meth) acrylates such as acrylate; and polyfunctional monomers such as methylene bis-acrylamide and the like. These may be used alone or in admixture of two or more.
[0018]
In the present specification, “... (Meth) acryl-” means “... acrylic-” and “... metacri-”.
[0019]
The ratio of N-vinyl-2-pyrrolidone (A) and monomer (B) is determined in consideration of the effect of the N-vinyl-2-pyrrolidone (A), and is appropriate for the film formed from the resin composition. N-vinyl-2-pyrrolidone (A) is 0.1% by weight or more, preferably 10% by weight or more of the monomer component, that is, the monomer (B) is 99. It is adjusted to be 9% by weight or less, preferably 90% by weight or less. Monomers (B) such as water solubility, oil solubility, stickiness, slipperiness, dryness, naturalness, film-forming properties, viscosity, transparency, gas compatibility, gas permeability, and compatibility with other additives In order for the effect of the above to be fully expressed, the monomer (B) is preferably 5% by weight or more, more preferably 10% by weight or more of the monomer component, that is, N-vinyl-2-pyrrolidone (A) is the monomer. Preferably, the component is adjusted to 95% by weight or less, more preferably 90% by weight or less.
[0020]
In order to produce the copolymer, a monomer component in which the amounts of N-vinyl-2-pyrrolidone (A) and monomer (B) are respectively adjusted is copolymerized. After the polymerization, the reducing compound (C) is added.
[0021]
By adding the reducing compound (C), a resin composition in which the odor estimated to be derived from the derivative of the decomposition product of N-vinyl-2-pyrrolidone (A) is sufficiently reduced is obtained in a state of a polymer solution. Can be easily obtained.
[0022]
Typical examples of the reducing compound (C) include hydrogen; carbon monoxide; sulfur dioxide; sulfites such as sodium sulfite and sodium bisulfite; sodium sulfide; hydroxyamines; alkali metals, magnesium, calcium, aluminum, and zinc. Metals such as, and amalgams of such metals; Metal salts such as iron (II), tin (II) titanium (III), chromium (II); Aldehydes; Reducing sugars such as maltose; Formic acid; Oxalic acid; Ascorbic acid, etc. These can be used alone or in admixture of two or more. Among these, hydrogen, sulfite, and reducing sugar are particularly preferable from the viewpoint of high safety, considering that the obtained resin composition is blended with a product for application to the human body such as cosmetics. preferable.
[0023]
The amount of the reducing compound (C) to be added is 0.0001 part by weight or more, preferably 0.01 part by weight or more with respect to 100 parts by weight of the monomer component, in order to sufficiently exhibit the reduction effect. In order to adjust and prevent the reducing compound (C) from remaining in a large amount in the resulting polymer solution and increasing the toxicity of the polymer solution, it is preferably 20 parts by weight or less, preferably 100 parts by weight or less, preferably Adjust to 10 parts by weight or less.
[0024]
The timing of adding the reducing compound (C) may be during the copolymerization of the monomer component or after the monomer component is copolymerized. Since (C) may shorten the life of the growing radical, it is desirable to add the reducing compound (C) after 1 hour, preferably after 3 hours from the start of copolymerization. Further, when the reducing compound (C) is added after the monomer component is copolymerized, if the polymerization temperature of the copolymer system is increased, the copolymer system may be appropriately cooled.
[0025]
The monomer component can be copolymerized in an aqueous solution or in an organic solvent. That is, a monomer component having a desired composition is sufficiently dissolved in purified water or an organic solvent, and a polymerization initiator is added while stirring with heating as necessary, and copolymerization is performed in an inert gas atmosphere. .
[0026]
The organic solvent is not particularly limited. For example, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol and propylene glycol; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; benzene and toluene Organic solvents usually used for solution polymerization, such as aromatics such as xylene, hydrocarbons such as n-hexane and cyclohexane, and acetates such as methyl acetate and ethyl acetate can be used. Among these, alcohols such as ethyl alcohol and isopropyl alcohol are particularly preferable in consideration of blending the resulting resin composition into cosmetics.
[0027]
When copolymerization is performed in the aqueous solution or organic solvent, it is preferable to adjust the concentration of the monomer component to about 10 to 80% by weight.
[0028]
The polymerization initiator is not particularly limited. For example, azo polymerization initiators such as azoisobutyronitrile, methyl azoisobutyrate, azobisdimethylvaleronitrile, dimethylazobismethylpropionate; peroxides such as benzoyl peroxide Physical polymerization initiators: Persulfate polymerization initiators such as potassium persulfate and ammonium persulfate can be used. The amount of the polymerization initiator may be about 0.01 to 5 parts by weight with respect to 100 parts by weight of the total amount of monomer components.
[0029]
The polymerization temperature at the time of copolymerization varies depending on the type of polymerization initiator to be used and cannot be determined unconditionally. However, it is usually preferably around the 10-hour half-life temperature of the polymerization initiator. In order to eliminate the possibility that unreacted N-vinyl-2-pyrrolidone (A) and / or monomer (B) may remain due to incomplete copolymerization, the polymerization time during the copolymerization is usually 5%. It is preferable to set it to about 20 hours.
[0030]
The presence or absence of unreacted monomers can be confirmed by measuring whether or not a double bond is present by a general analysis method such as the PSDB method (pyridine dibromide sulfate pyridine method).
[0031]
The viscosity average molecular weight of the copolymer thus obtained is not particularly limited, but is desirably about 1000 or more, preferably about 5000 or more so that the resin composition does not cause percutaneous absorption. It is desirable that the amount is about 3000000 or less, preferably about 1500,000 or less so as not to be distorted.
[0032]
The resin composition produced by the production method of the present invention has a characteristic odor significantly reduced as in the case of a conventional N-vinylpyrrolidone resin, and can form a film having appropriate hardness and gloss. Therefore, it can be suitably used for cosmetics for human bodies, for example.
[0033]
The cosmetic of the present invention is obtained by blending the resin composition. There are no particular limitations on the type of such cosmetic, but considering the effects of the resin composition, examples include cosmetics for scalp and hair.
[0034]
Examples of the scalp / hair cosmetics include hair tonic, pomade, hair spray, hair mist, mousse, gel, hair wax, shampoo, rinse, treatment, hair cream and the like.
[0035]
The amount of the resin composition in the cosmetic composition of the present invention is not particularly limited as long as the effect of the resin composition is sufficiently expressed. It is desired to be about 1 to 50% by weight, preferably about 3 to 30% by weight.
[0036]
In addition to the resin composition, the cosmetics of the present invention can be added to any components that are usually blended in cosmetics, such as emulsifiers, fragrances, preservatives, pigments, nutrients, moisturizers, depending on the type and purpose of the cosmetics. An ultraviolet ray inhibitor, a hair restorer, purified water, etc. can be appropriately blended according to a conventional method.
[0037]
Since the cosmetic composition of the present invention thus obtained contains the resin composition, it is a film having a specific hardness and gloss which is remarkably reduced as in the conventional N-vinylpyrrolidone resin. Can be formed.
[0038]
【Example】
Next, the N-vinyl-2-pyrrolidone-containing resin composition of the present invention, its production method, and a cosmetic comprising the same will be described in more detail based on examples, but the present invention is limited only to such examples. is not.
[0039]
Example 1
100 g of N-vinyl-2-pyrrolidone and 150 g of absolute ethanol are added to a 1 L reaction vessel equipped with a reflux condenser, a thermometer, a nitrogen gas inlet tube and a stirrer, and further 2,2′-azobisiso 0.1 g of butyronitrile and 0.05 g of ammonium persulfate were added, and the polymerization reaction was carried out by heating at 78-80 ° C. for 6 hours under a nitrogen gas stream while stirring.
[0040]
Next, 250 g of purified water was added to the polymerization reaction system and heated, 250 g of the solvent was concentrated, and 250 g of purified water was newly added to obtain a polymer solution. The polymer solution was cooled to 50 ° C., 0.5 g of sodium hydrogen sulfite was added and stirred to obtain a 20 wt% polymer solution (resin composition).
[0041]
The viscosity average molecular weight of the copolymer in the obtained polymer solution was 181,000.
[0042]
Example 2
A uniform solution by adding 80 g of N-vinyl-2-pyrrolidone, 20 g of hydroxypropyl methacrylate and 300 g of purified water to a 1 L reaction vessel equipped with a reflux condenser, a thermometer, a nitrogen gas inlet tube and a stirring device. Thereafter, 0.3 g of azobisdimethylvaleronitrile was further added, and the mixture was heated at 65 to 70 ° C. for 5 hours under a nitrogen gas stream with stirring to carry out a polymerization reaction.
[0043]
Next, 0.5 g of hydroxyamine and 200 g of purified water were added to the polymerization reaction system, and the mixture was stirred until it was uniform. Then, 100 g of water was concentrated under reduced pressure, and a 20 wt% polymer solution (resin composition) Got.
[0044]
The viscosity average molecular weight of the copolymer in the obtained polymer solution was 59,000.
[0045]
Example 3
A polymerization reaction was carried out in the same manner as in Example 2.
[0046]
Next, 0.1 g of 5% palladium carbon (50% wet) was added to the polymerization reaction system, and the reaction vessel was pressurized to 0.005 MPa with hydrogen and stirred at 25 ° C. for 5 hours. Thereafter, the polymerization reaction system was filtered to obtain a polymer solution (resin composition) having a concentration of 20% by weight.
[0047]
The viscosity average molecular weight of the copolymer in the obtained polymer solution was 59,000.
[0048]
Example 4
In a 1 L reaction vessel equipped with a reflux condenser, a thermometer, a nitrogen gas inlet tube and a stirrer, 50 g of N-vinyl-2-pyrrolidone, 20 g of N, N-dimethylaminoethyl methacrylate, N-methacryloyloxyethyl- After adding 30 g of N, N-dimethylammonium-α-N-methylcarboxybetaine and 250 g of purified water to obtain a homogeneous solution, 0.5 g of dimethyl-2,2-azobis (2-methylpropionate) was further added. The polymerization reaction was carried out at 70 ° C. under a nitrogen gas stream while stirring, and 300 g of purified water was added after 10 hours of polymerization.
[0049]
Subsequently, 150 g of water was concentrated by reducing the pressure of this polymerization reaction system, and 1 g of ascorbic acid was added and stirred uniformly to obtain a polymer solution (resin composition) having a concentration of 20% by weight.
[0050]
The viscosity average molecular weight of the copolymer in the obtained polymer solution was 477,000.
[0051]
Example 5
In a 1 L reaction vessel equipped with a reflux condenser, a thermometer, a nitrogen gas inlet tube and a stirrer, 70 g of N-vinyl-2-pyrrolidone, 15 g of n-butyl acrylate, 15 g of stearyl methacrylate and 150 g of absolute ethanol were added. After adding a uniform solution, 0.5 g of 2,2′-azobisisobutyronitrile is further added, and a polymerization reaction is carried out at 70 ° C. under a nitrogen gas stream while stirring. Thereafter, 0.3 g of benzoyl peroxide was added, and the polymerization reaction was further performed for 5 hours.
[0052]
Next, 200 g of purified water was added to the polymerization reaction system, and the mixture was stirred until uniform, and then 200 g of water was concentrated under reduced pressure. Thereafter, 5 g of maltose was added and stirred uniformly to obtain a polymer solution (resin composition) having a concentration of 20% by weight.
[0053]
The viscosity average molecular weight of the copolymer in the obtained polymer solution was 134,000.
[0054]
Comparative Example 1
After adding 100 g of N-vinyl-2-pyrrolidone and 100 g of absolute ethanol to a 1 L reaction vessel equipped with a reflux condenser, a thermometer, a nitrogen gas inlet tube and a stirrer, a uniform solution was added. 2,2'-azobisisobutyronitrile was added and the polymerization reaction was carried out by stirring at 70 ° C. for 10 hours under a nitrogen gas stream while stirring.
[0055]
Next, 200 g of purified water was added to the polymerization reaction system to obtain a uniform solution, and then 200 g of the solvent was concentrated under reduced pressure. After that, 300 g of purified water was added and stirred uniformly to obtain a polymer solution (resin composition) having a concentration of 20% by weight.
[0056]
The viscosity average molecular weight of the copolymer in the obtained polymer solution was 153000.
[0057]
Comparative Example 2
N-vinyl-2-pyrrolidone 90 g, diacetone acrylamide 10 g and purified water 400 g were added to a 1 L reaction vessel equipped with a reflux condenser, a thermometer, a nitrogen gas inlet tube and a stirrer. Thereafter, 0.1 g of azobisdimethylvaleronitrile and 0.1 g of potassium persulfate were further added, and the mixture was stirred and heated at 70 ° C. for 10 hours under a nitrogen gas stream to carry out a polymerization reaction.
[0058]
Subsequently, 200 g of the solvent was concentrated from the polymerization reaction system under reduced pressure, and 200 g of purified water was newly added to obtain a polymer solution (resin composition) having a concentration of 20% by weight.
[0059]
The viscosity average molecular weight of the copolymer in the obtained polymer solution was 699000.
[0060]
Test example 1
A polymer solution having a concentration of 20% by weight obtained in Examples 1 to 5 and Comparative Examples 1 and 2, and a polymer solution having a concentration of 2% by weight obtained by diluting the polymer solution having a concentration of 20% by weight with purified water 10 times. A sensory test was conducted for odor.
[0061]
Put 50 mL of each polymer solution into a 100 mL glass wide-mouthed sample bottle, and check the odor at the bottle mouth on each panel of 20 men and women randomly extracted and evaluate based on the following evaluation criteria. received. A, B, C, D, and E shown below were ranked according to the number of persons evaluated. The results are shown in Table 1.
[Evaluation criteria]
○: Almost odorless.
Δ: Slightly scorching.
X: Strong burning smell.
[Rank]
A: The evaluation o is 15 or more, and there is no evaluation x.
B: Evaluation is 15 to 19 people, and evaluation × is 1 to 5 people.
C: Evaluation ○ is 10 to 14 people, and evaluation × is 1 to 10 people.
D: Evaluation (circle) is 5-9 persons, and evaluation x is 1-15 persons.
E: Evaluation (circle) is 4 or less, and evaluation x is 1-16.
[0062]
[Table 1]

[0063]
From the results shown in Table 1, the polymer solutions obtained in Examples 1 to 5 were almost odorless in both the 20 wt% concentration and the 2 wt% concentration, and the reducing compound (C) was Since it is added, it can be seen that the odor estimated to be derived from the derivative of the decomposition product of N-vinyl-2-pyrrolidone (A) is sufficiently reduced.
[0064]
In contrast, the polymer solutions of Comparative Examples 1 and 2 in which the reducing compound (C) is not used are decomposed products of N-vinyl-2-pyrrolidone (A) even if the concentration is 2% by weight. It is clear that a burning odor peculiar to the derivative of ## STR2 ## is considerably recognized, and a resin composition having a low odor cannot be obtained unless the reducing compound (C) is added.
[0065]
Formulation Example 1 [Scalp / hair cosmetic (mousse)]
Each component shown below was stirred and mixed at room temperature (about 24 ° C.) to prepare a stock solution.
[0066]

[0067]
Next, the stock solution was filled in an aerosol pressure vessel (full injection amount: 100 mL) and further liquefied petroleum gas as a propellant [ratio of stock solution to propellant (stock solution / propellant (weight ratio)) = 90/10]. By attaching an aerosol valve and a button to this, an aerosol-type scalp / hair cosmetic product was manufactured.
[0068]
The aerosol-type scalp / hair cosmetic obtained was sprayed in an appropriate amount by a normal method of use to remove bubbles from the palm and applied to the hair. As a result, no burning smell was recognized in the palm and hair.
[0069]
Formulation Example 2 [Scalp / Hair Cosmetic (Lotion)]
The following components were stirred and mixed at room temperature (about 24 ° C.) to prepare a lotion-type scalp / hair cosmetic.
[0070]

[0071]
Next, the lotion-type scalp / hair cosmetic was filled in a bottle-type hair lotion container (internal volume: 100 mL) to produce a lotion-type scalp / hair cosmetic.
[0072]
An appropriate amount of the obtained lotion-type scalp / hair cosmetic was applied to the hair by the usual method of use, but no burning smell was observed.
[0073]
【The invention's effect】
According to the production method of the present invention, the characteristic odor caused by N-vinyl-2-pyrrolidone can be sufficiently reduced. Therefore, the N-vinyl-2-pyrrolidone-containing resin composition produced by the production method is A cosmetic that has a low odor and also contains the N-vinyl-2-pyrrolidone-containing resin composition also has a low odor, and is suitable, for example, as a cosmetic for hair and scalp.

Claims (7)

Formula (I):

N-vinyl-2-pyrrolidone (A) represented by 0.1 to 95 % by weight and an ethylenically unsaturated double bond-containing monomer (B) 99 copolymerizable with the N-vinyl-2-pyrrolidone (A) In the process for producing a resin composition comprising a copolymer obtained by copolymerizing a monomer component containing .9 to 5 % by weight,
0.0001 to 20 parts by weight of the reducing compound (C) is added to 100 parts by weight of the monomer component during or after the monomer component is copolymerized ,
Preparation of the reducing compound (C) is hydrogen der Ru N- vinyl-2-pyrrolidone-containing resin composition. Formula (I):

In the process for producing a resin composition comprising a polymer obtained by polymerizing 100% by weight of N-vinyl-2-pyrrolidone (A) represented by:
0.0001 to 20 parts by weight of the reducing compound (C) is added to 100 parts by weight of the polymer during or after the polymerization of the polymer,
A method for producing an N-vinyl-2-pyrrolidone-containing resin composition, wherein the reducing compound (C) is a reducing sugar. Formula (I):

N-vinyl-2-pyrrolidone (A) represented by the formula: 0.1 to 95% by weight and an ethylenically unsaturated double bond-containing monomer (B) 99 copolymerizable with the N-vinyl-2-pyrrolidone (A) In a process for producing a resin composition comprising a copolymer obtained by copolymerizing a monomer component containing 9 to 5% by weight,
0.0001 to 20 parts by weight of the reducing compound (C) is added to 100 parts by weight of the monomer component during or after the monomer component is copolymerized,
A method for producing an N-vinyl-2-pyrrolidone-containing resin composition, wherein the reducing compound (C) is a reducing sugar. N- vinyl-2-pyrrolidone-containing resin composition produced by process according to any one of claims 1-3. A cosmetic comprising the N-vinyl-2-pyrrolidone-containing resin composition according to claim 4 . A cosmetic comprising an N-vinyl-2-pyrrolidone-containing resin composition, wherein the N-vinyl-2-pyrrolidone-containing resin composition is obtained by the following method.
Formula (I):

N-vinyl-2-pyrrolidone (A) represented by the formula: 0.1 to 95% by weight and an ethylenically unsaturated double bond-containing monomer (B) 99 copolymerizable with the N-vinyl-2-pyrrolidone (A) In a process for producing a resin composition comprising a copolymer obtained by copolymerizing a monomer component containing 9 to 5% by weight,
0.0001 to 20 parts by weight of the reducing compound (C) is added to 100 parts by weight of the monomer component during or after the monomer component is copolymerized,
The reducing compound (C) is sulfite. The cosmetic according to claim 5 or 6, which is a cosmetic for scalp and hair.